Method of revivifying adsorbents



July 26, 1932. E. B. MILLER METHOD OF REVIVIFYING ADSORBENTS Original Filed June 6. 1922 3 Sheets-Sheet 1 MN \N #Mu M9 July 26, 1932. E. B. MILLER .METHOD oF REVIVIFYING ADsoRBENTs Original Filed June 6- 1922 3 Sheets-Sheet 2 y Qnwmo@ W m aww@ @my E. B. MILLER METHOD 0F REVIVIFYINQv ADSORBENTS July 26, 1932.

Original Filed June 6, 1922 3 Sheets-Sheet 5 wuentofc Patented July 2,6, 1932 UNITED STAT-as PATENT OFFICE ERNEST B. MILLER, F BALTIMORR, MARYLAND, ASSIGNOR TO THE SILICA. GEL COR- PORATION, 0F BALTIMORE, MARYLAND, A CORPORATION 0F MARYLAND METHOD 0F REVIVIIYING ADSORBENTS Original application filed June 6, 1922, Serial No. 566,365, and in Sweden and Germany latch 10, 1923.

Divided and this application led June 12, 1928. Serial No. 284,876. l

The present invention relates broadly to a method for treating liquids to remove or recover substances therefrom, and more particularly to a method for revivifying an adsorbent used in the treatment of such liquids.

'In a prior application, Serial No. 544,186, filed March 16, 1922, in the name of Walter A. Patrick and Ernest B.l Miller, a process for refining oils has been described. A later applil cation, Serial No. 566,365, filed June 6, 1922,

by Ernest B. Miller, discloses and claims an apparatus for carrying out said process, and also defines certain methods for revivifying the adsorbent used in the process described in the earlier application.

This application is a division of the later application, Serial No. 566,365, and isdirected to a method for revivifying adsorbents used in the refining of oils and other analogous processes. Y l

Briefly stated, the method described in said earlier application consists in removing a substance from a solution by adsorbing the same in a porous material having pores of ultramicroscopic size, then liberating the substances adsorbed in the material, and, if desired, using the material over again for refining more solution. The substance liberated from the f' pores of the adsorbing material may be recovered if desired.

Thus, the liquid to be refined is brought into intimate contact with the adsorbing material,'whereby the substances in solution are adsorbed in the pores of the material. Then the material is freed of the substances adsorbed in its pores. One method of accomplishing this consists in bringing the material into contact with a liquid which has a lower surface tension toward the adsorbing material then toward the substances in the pores thereof, and thereafter suitably treating the material to drive o the liquid thus adsorbed in its pores. Finally, the material, being fully 5 activated, may be returned for use again. f

The objects and features of novelty of the invention will be apparent from the description taken in connection with the drawings, in which:

Figure 1 is a diagrammatic view illustrating in elevation one form of apparatus constructed for use in connection with the present I of agitator that may be employed in the ap-v paratus;

Figure 3 is a sectional elevation of one form of a separator which may be used in the apparatus; v

Figure 4 is a sectional view taken substantially on the line 4-4 of Fig. 1 showing the feed device; and

Figure 5 is a longitudinal sectional elevation through one form of activator that may be employed.

Before describing the present method and the apparatus for carrying out the same, the methods of said prior applications will be briefly mentioned, in order to obtain a better understanding of the present invention. Ac cording to said-prior applications, dissolved substances may be adsorbed from a solution under certain conditions by means of a porous material having very fine or ultramicroscopic pores. The pores of the adsorbing material required are so small that it is a very difficult matter to accurately determine and deline their size. For this purpose, however, reference may be had to the amount of Water that one gram of material will adsorb when exposed to Water vapor under definite conditions of temperature and partial pressure of water vapor. v

The amount of water adsorbed by a porous body at a given temperature and partial pressure depends both upon the size of the pores and upon the total interior volume of the pores. By determining the amount of a given fluid, Water for example, which may be adsorbed by each of the porous bodies under the same conditions of temperature and partial pressure, We have a means of comparing the size and volume of the pores in the two adsorbents. For example, one gram of silica gel has a total internal volume of about 0.41 cc. In other words, if We completely fill the pores in silica gel with Water, the amount of water taken up VWill be approximately 41% of the initial weight of the gel. A sufficient percentage of the tot-al internal volume in silica gel is made up of pores of such size that the gel will adsorb at C. at least 21% of its own weight of water at a partial pressure below 22 nun. Kieselguhr and boneblack under the above conditions will adsorb practically no Water. Highly lactivated charcoal, such as cocoanut charcoal, will adsorb a relatively large amount of Water. It follows, therefore, that liieselguhr and boneblack have practically no pores as small as the greater part of the pores in silica gel. On the other hand, highly activated charcoal has many small pores.

It was found that materials which adsorb less than about 10% of their initial Weight ot Water at 30 C. and at a partial pressure not exceeding 22 mm. of mercury have pores too large to be of any practical value in adsorbing solutes from solutions. The invention, therefore, includes only materials having a sufficient number of small pores so that they will adsorb not less than 10% of their initial Weight of Water at 30o C. and at not exceeding a partial pressure of 22 mm. of

mercury.

The material preferred for practicing said methods is silica gel. This is a glass-hard material having ultramicroscopic pores and may be heated as high as 700o (i. without injury. In cases Where silica gel is not suitable, other hard porous gels or adsorbing material may be used, provided they have a sutlicient number of small pores as defined above, i. e. activated charcoal, gels of iron oxide, tin oxide, aluminum oxide, tungsten oxide, zirconium oxide and titanium oxide.

The silica gel preferably employed as an adsorbing material is said methods and the present invention is made in accordance With U. S. Patent 1,297,724 to Patrick, and should be distinguished from the dried gelatinous precipitate obtained, for example, by mixing an acid and sodium silicate and then drying. This latter product does not have the porous structure required and is not suitable to adsorb solutes from solutions to any practicalVA extent.

According to said prior applications, the liquid is refined by bringing the crude product into intimate contact with an adsorbing material having pores of a size to adsorb the substances in solution, the material preferably being in powdered condition; allowing the liquid and a-dsorbing material to remain in contact. until the said substances are adsorbed by the material and thereafter separating the refined product from the material. Itis also desired to liberate the adsorbed substances from the adsorbing material, such as silica gel, so that it may be used over again. As described in application Serial No.

566,365, according to one method, this is accomplished by driving out the substances` adsorbed in the adsorbing material by immersing the material in a liquid that has a lower surface tension at an interface with the adsorbing material than the substances adsorbed, so that the latter are replaced by the liquid; and then activating the material by driving off or liberating the liquid. For the products having higher boiling points, this Wash is not sufficient, and 1n a dition steam activation may be employed.

Referring to Fig. 1, the liquid to be refined, such as a petroleum product, is supplied to a pump 10 by a pipe 11, and this pump through the pipe 12 feeds the petroleum product into an agitator 13. This agitator may be of any suitable construction, the function being to bring the adsorbing material and liquid into intimate contact. As shown in Fig. 2, it may consist of a closed vessel 14 having a vertical shaft 15 provided with blades 16, said shaft projecting above the top of the vessel and having a pulley 17 whereby the shaft is rotated. Suitable pulverized adsorbing material, such as the silica gel previously mentioned, is supplied through the pipe 18 to the agitator so that the petroleum product and gel are thoroughly mixed. The mixture is continuously discharged through the pipe 19 to a separator 20. As shown in Fig. 3, this separator, the function of which is to separate the adsorbing material from the liquid, consists of' a closed top vessel having a slightly conical bottom provided with an outlet. A shaft is disposed vertically in the vessel and adjacent the bottom thereof has the deflectors 21 for forcing the adsorbing material, which settles at the bottom, toward the outlet. Around the top of the vessel is a launder 22. The adsorbing material settles to the bottom of the tank and is discharged through the outlet, while the petroleum product flows into the launder and is carried bya pipe 23 to an agitator 132, and a pump 24 acts to continuously supply adsorbing material to said agitator 132. The mixture is discharged from this second agitator through a pipe 25 to a secondseparator 202. In the same manner as previously described, the adsorbing material settles to the bottom of this separator, and the petroleum is discharged through a pipe 23 into a third agitator 133, This agitator is supplied With freshly activated adsorbing material from a hopper 27. The mixture from the agitator is conveyed by the pipe 28 to a third separator 203. The refined petroleum product is discharged from this separator through a pipe 29. The adsorbing material which settles to the bottom of the thirdl separator is discharged through the outlet in the bottom and conveyed by the pipe 30 to the pump 24, previously mentioned, this pump acting to vcause the flow of the adsorbing material. The adsorbing material discharged at the bottom of the second or middle separator is conveyed by a pipe 31 to a pump 45 which discharges into the pipe 18 previously mentioned. This pump 45 effects the ow in the pipe 31. f

Although an apparatus having three units, each unit "consisting of an agitator and a l separator, has been described, the invention is not limited to any particular number of f units.

It will be noted that the fresh, or activated gel is fed into the system to act on i-he product being refined ]ust before it is A final y discharged, and then its path through the apparatus is from the discharge end toward-the inlet end. Thus the product fed into the first agitator 13 is mixed with adsorbing material that has already passed through a plurality of separators. This counter-How of the adsorbing material andv the petroleumproduct to be refined gives a very efficient action.

The adsorbing material settling in the bottom of the irst separator 2O is dischar ed into a pipe 33. This adsorbing material as adsorbed impurities from the petroleum product and, of course, has petroleum product associated therewith. In order to make the process continuous, it is now necessary to free the adsorbingV material from its adsorbed substances or activate it. The objectionable substances removed by the adsorption often consist of or contain complex organic compounds, usually associated with sulphur, which, on heating to a sufficiently high temperature to volatilize them, undergo decomposition in the gel, frequently with deposition of carbonaceous and gummy materials, diiiiult to remove from the gel. Satisfactory activation may be effected either by washing with hot Water previous to introduction into the activator or by simply distilling the adsorbed material from the gel in a current of steam or other non-oxidizing gas, the object being to reduce the temperature necessary to get rapid distillation and thus avoid the decomposition referred to above, which would occur at a higher temperature. This latter method is claimed in application Serial No. 566,664, filed June 7, 1922.

In all phenomena in connection with the adsorption by solids from liquids, the surface tension at the interface between the solid and the liquid is one of the most important factors determining the degree of adsorption. Since the adsorbing materials used in the present invention always contain water, the surface tension at the interface of gel and water will be zero and, therefore, less than the surface tension at the interface of the porous material and other liquids. Accordingly, such porous materials for example gels, will adsorb water in preference toany other liquid. When a gel which has been saturated with gasoline, for example, (or other liquid immiscible with water) is brought in contact 65 with water, the latter will be adsorbed and the gasoline driven out. If the contact is maintained long enough, the vdisplacement of gasoline by water will become complete. Furthermore, this water displacement of adsorbed oils may be accelerated by working at a higher temperature.

yIt has been further discovered that when a gel having adsorbed in it a mixture of hydrocarbons, such as is obtained by bringing gels in contact with kerosene, is treated with water, the lighter hydrocarbons are driven out more rapidly than the heavier fractions, particularly if the water is cold. The products associated with the gel are, therefore, recovered in fractions, which is a very desirable method inasmuch as the most objectionable `constituents inunrefined gasoline, which any process of refining seeks to remove, appear to consist largely of high-boiling hydrocarbons containing sulphur. Accordingly, the lighter and more valuable fractions of the adsorbed liquid may be displaced by agitation for a limited time with cold water and the liberated substance drawn off. The heavier fractions, incluing most of the objectionable sulphur compounds and other impurities, are liberated by agitation, repeatedly if necessary, with hot water.4 The oil recovered by cold water displacement is usually of about the same qualityas the original unrefined distillate and may be re-run. The very much smaller fraction recovered by hot water agitation consists of relatively high-boiling constituents running high in sulphur and unsaturated byhydrocarbons, and is suitable for a 10 flotation or fuel oil. This fraction, regardless of its sulphur content, is unsuitable for burning as kerosene.

The product containing over 25% unsaturated hydrocarbons obtained from the pores 10| of an adsorbing material saturated by rening a petroleum product, is new. It is free from sulphuric acid and may run as high as 7 5% or more unsaturated hydrocarbons. Perhaps it may best be deiined as the product obtained from the pores of a porous material having pores of a size to adsorb not less than 10% of its own weight of water at 30 C. when exposed to water vapor at a partial pressure substantially not exceeding 22 mm. of mercury, which material has been used in refining a petroleum product. This new product is particularly adapted for use as a iiotationv oil in the flotation process of Vrecovering metals, because it has such a high percentage of unsaturated hydrocarbons.

The gel, or other porous material employed, having been freed by water displacement of the hydrocarbons and other constituents adsorbed from the liquid being refined, is removed from the wash water, iiltered, and the resulting gel cake which now contains prac- 'tically nothing but water, is run into an activator and its Water content reduced to the las 34 whlch -discharges into a water Wash agita- `tor 35 of the same construction as the other agitators. Cold Water is supplied to this agitator through a pipe 35 so that the gel 1s i thoroughly mixed with the water for the purheads 102.

pose of driving out the substances adsorbed in the refilling described above. This agitator discharges through a pipe 36 into a separator 37 of the same construction as the other separators, in which the gel settles to the bottom and gasoline or other petroleum products liberated from the gel arecarried by the pipe 38 to the agitator 13 so that these products are again run through the refining process. The gel which settles to the bottom of the separator 37 is carried by pipe 39 to the pump 32 which discharges into another agitator 41 supplied with hot Water by the pipe 42. This agitator discharges the mixtures into another separator 44. The fraction recovered by this vhot water agitator 41, consisting of relatively high-boiling constituents, is discharged through the pipe 46, and may be used for fuel oil, or as a flotation oil. The gel which settles to the bottom of the tank 44 is carried by pipe 47 to pump 48 and discharged through pipe 49 to a filter press 50 of any suitable construction. In this press the surface water is filtered out, and the gel cake discharged through the -pipe 51 to an activator 52. y

This activator is illustrated in Fig. 5. Briefly stated, it comprises a cylindrical shell 100 with tubes 101 connecting the opposite The shell is provided with circumferential rings 103 supported by rolls 104 (Fig. 1) whereby the cylinder as a Whole may be rotated. Hot gases are supplied through the pipef122 which has communication with the chamber 106. This chamber in turn is inv communication with the interior of the tubes 101 so that the hot gases pass through the tubes to the chamber 107 at the opposite end of the cylinder. This charnr is in communication with a. suction fan 109 Fig.-1) having the outlet pipe 108. The

ladsorbing material to be activated is supplied through the conduit 51. If necessary, water, or steam, or other gas may besupplied to the interior of the activator through the inlet 110 which has communication with the centrally ydisposed tube 111 secured to the head 102. Usually, however, there is suf-4 licient water in the adsorbing material supplied to the activator 52 so that the steam necessary for distilling out any of the adsorbed substances not displaced by the Water wash is supplied from this source. The aims of the arrangement are to prevent ingress of air to the activator and to have any residual adsorbed substances distilled out of the pores of the adsorbing material. If heat as furnished by the hot gases alone is employed for activating the adsorbing material, there is danger of clogging the pores of the adsorbing material by the deposition of carbonaceous and gumrny materials. T his does not occur Where air is excluded from the activator.

, The dried adsorbing material is discharged through the duct 112a into the intake of the fan 54. The pipe 53 from the fan discharges the gel or adsorbing material into a cyclone separator 55 wherein the gel settles to the bottom and is discharged into a hopper' 56 from which it is fed by a screw conveyor 60 to the hopper 27 which discharges into agitator 133 thereby. returning the gel into the refining cycle. If desired, the gel may be cooled andvfor this purpose the hopper 27 has its upper portion constructed With cooling surfaces. The vapors separated out by the cyclone separator 55 may be discharged into the atmosphere, or, if it is desired to recover any of the vapors, they pass through a pipe 57 to a condenser 58. The condensate and gel not separated by the cyclone separator 55 are drained through a pipe 59 to a pump 60l which discharges through a pipe 61 into the water. Wash agitator 41.

It is desirable to prevent the passage of vapors through the lower end of the cyclone separator 55. This may be accomplished in any suitable manner. As shown, a novel form of feeding device is employed. Referring to Fig. 4, this device comprises a plate 85 carried by an oscillating shaft 86 disposed inthe box 87, having a hopper bottom 56. The plate 85 is disposedhorizontally and is counterbalancedl by the weight 88. As shown in Fig. 1, the plate is disposed a slight distance below the lower end of the outlet of the cyclone separator 55. The plate is oscillated back and forth in a horizontal plane in any suitable manner, but the extent of oscillation is not sullicient to move the plate from beneath the lower end of the cyclone separator at any time. For the purpose of oscillating the shaft 86 any suitable mechanism may be employed. As shown, an arm 89 is secured to the upper end of the shaft and outside the box 87. This arm is connected by a link 90 to a crank pin 91 on the crank disk 92, the latter being carried `by the armature shaft 93 of the motor 94. In

over again, and a greater volume of vapors is supplied to the fan so thatthe velocity in i the pipe 53 is suiiicient to raise the adsorbcycles through the apparatus, that its adsorbing efficiency will be decreased beca-use of the deposition of carbonaceous or gummy materials thereon. -Where this is liable to occur, an auxiliary activator may be employed to drive oif these substancesl from the adsorbing material.

As shown, this auxiliary activator, in the form of the drum 120, isdisposed in the furnace 121 which supplies hot gases through the pipe 122 to the main activator 52. Adsorbing material taken fromthe hopper 56 or other point may be carried through pipe 123 to the inlet end of the activator 120. This pipe may be supplied with a valve or damper 124 to control the flow of adsorbing material therein. At its discharge end, the auxiliary activator 120 has a blower 125 discharging through pipe 126 into a cyclone separator 127. The adsorbing material discharged through this pipe 126 is separated from the air and gases in the cyclone separator 127 and discharged into the cycle at any suitable'point, as the Worm conveyor 60. The vapors from the top of the cyclone 127 are returned by ypipe 128 to the activator 120 at .a point adjacent the inlet of the blower 125. In this manner these vapors are used over and over to raise the activated adsorbing material. A small quantity of the vapors Imay be exhausted through pipe 128', and the loss made up by air supplied through pipe 123 at the inlet end of the activator. In this manner oxygen is obtained to burn the carbonaceous deposits associated with the materi al. It will beunderstood that `the quantity of adsorbing material supplied to this auxiliary activator may be regulated by valve 124. If desired, all of the adsorbing material from hopper 56 may be passed at intervals through the auxiliary activator 120.

Liquids having relatively low boiling points, such as gasoline, kerosene and benzol may be refined With or without the step of washing the adsorbing material to displace the adsorbed substances as described above. Other liquids, such as petroleum products having higher boiling points are preferably refined Without the wash step, the activation g being effected by a hot non-oxidizing gas such as steam, carbon dioxide, nitrogen, etc.

The apparatus would be like that shown by Fig. 1 except that the parts Jfor the Washing step are omitted. Thus the adsorbing material'y separated out from the separator 20 would be conveyed directly to the ilter 5'0 by means of a pipe, and this iilter discharges into the activator 52. A non-oxidizing gas such as steam may be supplied to the activator through the gas inlet 110, it being the object in activating most materials, as in the apparatus shown in Fig. 1, to exclude air from the activator. The steam supplied through pipe 110 distills out the substances adsorbed in the pores of the adsorbin material and at the same time prevents te ingress of air. If hot gases from furnace 121 alone were employed for activating and air were admitted to the activator, the volatile hydrocarbons liberated by the activation in the case of gasolines, benzols and kerosene would lbe liable to combine with the air in the discharge pipe from the activator or in the separator 55 causing explosion. This is prevented by excluding the air from the activater. f It will be understood that hot gases may be supplied from the furnace 121 to heat the activator if necessary.

If desired, an auxiliary activator like that described in connection with Fig. 1 may be employed. It may be arranged in the same location as shown in Fig. 1 and therefore needs no further description.

It will be understood that the term vapor throughout the specification and claims includes gases as well as vapors.

Although a specific form of the invention has been described in de tail,l it will be understood thatthe invention is not 'thus limited but includes modifications and changes which come within the scope of the appended claims.

Having thus described the invention, what is claimed as new and desired to be secured by Letters Patent is:

1. The method of revivifying a porous gel having pores of such size that it will adsorb not less than 10% of its own weight of water at 30 C. and at a partial pressure of 22 mm. of mercury which is charged with an adsorbate obtained in the reiining of petroleum products consisting in contacting the Agel without previous treatment with Water for a sufiicient time to cause an exchange of the water and adsorbate, thereby displacing the adsorbate from the gel.

2. The method of revivifying silica gel charged with an adsorbate obtained in the refining of petroleum products consisting in contacting the vgel Without previous treatment with water for a sufficient time to cause an exchange of the water and adsorbate, thereby displacing the adsorbate from the 3. The method of revivifying a. porous gel 'having pores of such size that it will adsorb not less than 10% of its own Weight of Water at 30 C. and a partial pressure of 22 mm. of mercury which is charged with an adsorbate obtained in the refining of petroleum products comprising different fractions consisting in .contacting the gel without previous treatment with water to cause anexchange of the water and adsorbate thereby displacing one of the fractions of the adsorbate, and a ain contacting the gel with water at a higher temperature thereby displacing the other fraction of the adsorbate.

4. The method of revivifying silica gel charged with an adsorbate obtained in the rening of petroleum products comprising different fractions consisting in, contacting the gel without previous treatment with. water to cause an exchange of the water and adsorbate thereby displacing one of the fractions of the adsorbate, and again contacting the gel with -water at a higher temperature thereby displacing the other fraction of the adsorbate. v

5. The method of revivifying a porous gel having pores of such size that it will :adsorb not less than 10% of its own weight of water at 30 C. and at a partial pressure of 22 mm. of mercury which is charged with an adsorbate obtained in the refining of petroleum products consisting in contacting the gel v without previous treatment with water for a sufficient time to cause an exchange of the water and adsorbate, thereby displacing the adsorbate from the gel, and removing the water from the gel.

6. The method of revivifying a porous gel having pores of such size'that it will adsorb not less than 10% of its own weight of water at 30 C. and a partial pressure of 22 mm. of'mercury which is charged with an adsorbate obtained in the refining of petroleum p roducts comprising different fractions consisting in contacting the gel without previous treatment with water to cause an exchange of the water and adsorbate thereby displacing one of the fractions of the adsorbate,

again contacting the gel with water at a higher temperature thereby displacing the other fraction of the adsorbate, and removing the water from the gel.

In testimony whereof I hereunto aix my signature.

ERNEST YB. MILLER. 

